A kinetic study of vapor-phase cyclohexene epoxidation by H2O2 over mesoporous TS-1

被引：55
作者：
Kwon, Stephanie [1 ]
Schweitzer, Neil M. [1 ]
Park, Sunyoung [1 ]
Stair, Peter C. [2 ,3 ]
Snurr, Randall Q. [1 ]
机构：
[1] Northwestern Univ, Dept Chem & Biol Engn, Evanston, IL 60208 USA
[2] Northwestern Univ, Dept Chem, Evanston, IL 60208 USA
[3] Argonne Natl Lab, Chem Sci & Engn Div, Argonne, IL 60439 USA
来源：
JOURNAL OF CATALYSIS | 2015年 / 326卷
基金：
美国国家科学基金会;
关键词：
Alkene; Oxidation; Zeolite; Hydrogen peroxide; Compensation effect; AQUEOUS HYDROGEN-PEROXIDE; GOLD/MESOPOROUS TITANOSILICATE CATALYST; TITANIUM-BASED EPOXIDATION; DENSITY-FUNCTIONAL THEORY; PROPYLENE EPOXIDATION; HETEROGENEOUS CATALYSIS; OXIDATION; O-2; H-2; DECOMPOSITION;
D O I：
10.1016/j.jcat.2015.04.005
中图分类号：
O64 [物理化学（理论化学）、化学物理学];
学科分类号：
070304 ; 081704 ;
摘要：
A kinetic analysis of gas-phase cyclohexene epoxidation by H2O2 over mesoporous TS-1 was performed. The production of cyclohexene oxide was very stable with high selectivity. Based on the kinetic analysis, the gas-phase mechanism is proposed to be similar to that of the liquid-phase reaction: an Eley-Rideal type mechanism, in which the reaction between a Ti-OOH intermediate and the physisorbed alkene is the rate-determining step. When the partial pressure of water or H2O2 was varied, a compensation effect was observed. Based on the kinetic model, the compensation effect is attributed to variations in the surface coverage of intermediates, specifically the competitive adsorption of water and H2O2 at the Ti active sites. A meaningful activation energy can only be obtained at high surface coverages of H2O2 and was determined to be 40 +/- 2 kJ/mol. (C) 2015 Elsevier Inc. All rights reserved.
引用
收藏
页码：107 / 115
页数：9
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